Azo compounds and material colored therewith



Patented a. 9, 1 94s AZO COMPOUNDS 2,386,599 AND MATERIAL COLOREDTHEREWITH Joseph B. Dickey and James G. McNally, Rochester, N. Y.,assignorsto Eastman Kodak Company, Rochester, N. Y., a corporation ofNew v Jersey No Drawing. Application April 22, 1943, Serial No. 484,079

Claims. (Cl. 260-155) This invention or discovery relates to new azocompounds and their application to the art of dyeing or coloring.Textile materials such as organic derivatives of cellulose, wool, silk,nylon and lacquers composed of cellulose esters and cellulose ethers,tor example, can be colored. Coloration can be efiected by dyeing,printin stenciling or other suitable methods.

Typical organic derivatives of cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such as celluloseacetate, cellulose formate, cellulose propionate, or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organic acid estersof cellulose such as cellulose acetate-propionate, celluloseacetate-butyrate, and the cellulose ethers such as methyl cellulose,ethyl cellulose, or benzyl cellulose. While our invention or discoverywill be illustrated more particularly inconnection with the colorationof. cellulose acetate, a material to which the invention or discovery isespecially adapted, it will be understood that it applies equally to thecoloration of the other materials just mentioned.

It is an object of our invention or discovery to provide a new class ofazo compounds. Another object is to provide a process for the dyeing orcoloration of various textile materials including organic derivative of.cellulcse, wool, silk and nylon textile materials. A further object isto provide dyed textile materials which are of good tastness to lightand washing and-which can be readily discharged to a pure white. A stillfurther object is to provide dye compounds having improved dyeingproperties as regards levelness and speed of dyeing at relatively lowtemperatures. A further object is to provide a satisfactory process forthe preparation of the azo compounds of our invention or discovery.Other objects will appear hereinafter.

The azo" compounds of our invention or discovery by means of which theabove objects are accomplished or made possible consist of theazocompounds having the formula:

R,-N=NR1 wherein R represents the residue of a member selected from thegroup consisting of a benzene broadly to the azo compounds having theabove formula, it relates more particularly to the azo compounds havingthe formula:

wherein X represents a member selected from the group consisting ofhydrogen, a hydroxy group, an alkoxy group, an alkyl group, a cyanogroup,

a halogen atom, a nitro group, a sulfonealkylgroup, asulfonehydroxyalkylamide group, and an alkylsulfone group, R1 stands forthe residue of a benzene nucleus and Rs stands tor a member selectedfrom the group consisting of hydrogen, an alkyl group, an alkoxyalkylgroup, a hydroxyalkyl group, and an unsaturated openchain hydrocarbongroup whose unsaturation consists of a double bond.

The azo compounds of our invention or dismore particularly directed.

covery constitute valuable dyes for the coloration of materialshereinbefore named especially for the coloration of cellulose acetateand nylon. For the coloration of organic derivative of cellulose textilematerials,' nuclear non-sulfonated compounds should be employed and itis to such compounds that our invention or discovery is These compoundslikewise can be used to color the other materials named herein. Nuclearsulfonated compounds 0f the invention or discovery which can be preparedby sulfonation of the unsulfonated compounds or by the use of sulfonatedintermediates possess little or no utility for the coloration of organicderivative of cellulose textile materials but can be used to color wooland silk. 7

The azo dye compounds of our invention or discovery possess goodaflinity for the fiber and in many cases dye cellulose acetate, forexample, more rapidly than the corresponding dye compounds containing agroup such as p-hydroxyethyl, for example, other than 4,5-dihydroxyamyl.Further, in many instances the dye compounds of the present invention ordiscovery are more light last than the corresponding dyes not containinga 4,5-dihydroxyamyl. group. Aiso,"as well known in the art, it isdifiicult to prepare azo dyes yielding dischargeable violet, purple, andblue shades on organic derivative of cellulose which dye rapidly andgive deep shades at 70-80, C. The dye compounds of our invention ordiscovery help to fill this need in the dyeing art, while at the sametime, because the 4,5-dihydroxyamyl group causes a shift in color to theblue, they yield shades that are bluer and deeper than any of thosehitherto known to the art from corresponding dye compounds containing agroup other than the 4,5-dihydroxyamyl group.-

Many other shades in addition to those just named, of course, areobtainable using the dye compounds described herein.

The azo compounds of our invention or discovery can be prepared bydiazotizing an aminobenzene, an aminonaphthalene, or an aminoazobenzenecompound and coupling the diazonium compound obtained with a couplingcomponent containing the 4,5-dihydroxyamyl group joined directly theretothrough a nitrogen atom. Also, the 4,5-dihydroxyamyl group can beintroduced into the dye molecule after formation of an azo compound. Toillustrate, 4 nitrobenzene 4- aminobenzene can be converted to4'-nitrobenzeneazo-4-mono-(4,5 dihydroxyamyl) amino benzene. Ordinarily,this latter procedure is not employed.

The 4,5-dihydroxyamyl group present in the azo compounds of ourinvention can be joined directly to the dye molecule through a nitrogenatom which is either a nuclear substituent or a part of the dye nucleus.Thus anilene and naphthylamine coupling components, the amino group ofwhich contains a 4,5-dihydroxylamyl group, or heterocyclic couplingcomponents such as 1,2,3,4- tetrahydroquinoline, benzomorpholine,benzothiomorpholine, 2,3-dihydrobenzopyrazole, lndole and indoline, thenuclear nitrogen atom of which contains a 4,5-dihydroxyamyl group can beemployed in the preparation of the azo compounds or the invention;

.The term alkyl as used herein and in the claims refers to unsubstitutedalkyl groups such as, for example, the methyl group, the ethyl group, apropoyl group or a butyl group. By hydroxyalkyl is meant groups, forexample, such as the resulting cyclic diazo compound is recovered byfiltration and washed with water;

.1 gram mole of l -(p-hydroxyethyb, 4,5-dihydroxyamyl-)amino-3-methylbenzene is dissolved 5 in an acetic acid solution and theresulting solution is cooled to a temperature of about 10 C. Thediazonium compound formed as described above is then added with stirringwhile maintaining the reaction mixture in a cooled condition.

Upon completion of the coupling reaction which takes place, the reactionmixture is poured onto ice and water and the precipitated dye compound Iis recovered'by filtration, washed with water and dried. It has theformula;

crnomon N10 N=N N crncnlcmoncmon H H: (5H

and colors cellulose acetate bright magneta shades which are very fastto light. This dye likewise colors the other materials named herein agenerally similar color.

EXAMPLE 2 .1 gram mole of 1-amin0-4-nitrobenzene-6-sulfone-mono-p-methoxyethylamide is diazotized in known fashion and thediazonium compound obtained is added to a solution of .1 gram mole oflene in dilute hydrochloric acid. Throughout the coupling reaction whichtakes place the reaction mixture is maintained at a temperature of about0-10" C. Following the addition of the diazonium solution, the reactionmixture is permitted to stand for awhile after which it is slowly madeneutral to Congo red paper by the addition of sodium acetate whereby'thecoupling reaction is 4 completed. The dye compoundislthen recoveredB-hydroxyethyl, p-hydroxypropyl, p,-y-dihydroxypropyl, 'y-hydroxypropyl,a-hydroxybutyl, 5-hydroxyamyl and 4,5-dihydroxyamyl. By falkoxyalky ismeant groups, for example,'such as p-methoxyethyl, ,e-ethoxyethyl,methoxypropyl,

6 methoxybutyl and ,6 ethoxy-p-ethoxyethyl. The term alkoxy is intendedto include groups such as methoxy, ethoxy, propoxy, butoxy,p-hydroxyethoxy and p-ethoxyethoxy. Typical of the unsaturated openchain hydrocarbon groups whose unsaturation consists of a double bond" 0may be mentioned -on,on=cm, -oH,c=oH,, -cnlomcn=orn -OH:CH=CHCH:

EXAMPLE 1 .1 gram mole of 1-amino-2-hydroxy-4-nitrobenzene is diazotizedin the usual manner and and - by filtration, washed with water anddried. It has the formula:

H N-CHaCHzCHgCHCHaOH and colors cellulose acetate greenish-blue. Theother materials named herein are likewise colored a generally similarshade.

EXAMPLE 3 .1 gram mole of l-amino-2,4-dinitro-B-monoethylsulfoneamide isdiazotized in known fashion and the diazonium compound obtained iscoupled in a cold acetic acid solution with .1 gram mole of N-4,5dihydroxyamyl 2,7 dimethyl- 1,2,3,4 tetrahydroquinoline. The desired dyecompound is precipitated by pouring the reaction mixture onto'a mixtureof ice and water and recovered by filtration following whichit is washedwith water and dried. The dye compound obtained has the formula:

cmcnicmcncmon Y n H v NO on N\ I c cn NO N=N O=.'N-CzHl1-4,5-dihydroxyamylamino 5-hydroxynaphtha-' shades.

H v v 2,380,096 I a and colors cellulose acetate blue. Generally imilarcolorations are obtained on the other materials indicated herein.

.1 gram mole of p-nltroaniline is diazotizedand 'the diazonium compoundobtained is added to a cold dilute hydrochloric acid solution of .1 grammole of 14,5-dihydroxyamylamino-2-chlorobenzene. The coupling reactionwhich takes place is completed by adding sodium acetate until thereaction mixture is Just neutral to Congo red paper. The dye compoundiormed is recovered by filtration, washed with water and dried. It

has the iormula: V

. E. v rim-Om -cmcmcn,cncmon EXAMPLE 6 .1 gram mole ofl-amino-Z-fluoro-d-nitrobenzene and the diazonium compound obtained iscoupled with .1 gram mole of N-4,5-dihydroi:yamyl-l,2,3,4-tetrahydroquinoline. The dye compound obtained has theiormula:

(fHrCHaCHsC HCHrOB N H I F I and colors cellulose acetate deepbluish-red shades. 7

j Exmnr'l .1 gram mole of -l-amino-2-hydroxy-4-nltrobenzene isdiazotized and the diazonium compoundobtained is coupled with .1 grammole oi N-4,'5-dihydroxyamylbenzomorpholine. The dye compound obtainedhas the formula:

and colors cellulose acetate pinkish-red shades.

ExAIPLI-S .1 gram mole oi diazotized 2,4-dinitroaniline is coupled with.1 gram mole of l-4,5-dihydroxysmynmmo s hydroxynaphthalene. The dyecompound obtained has the formula:

and colors cellulose acetate greenish-blue shad cs. 11' 1-4.5dihydroxyamylamino 2 methoxy-5- methylbenzene is used as the couplingcomponent in this example, the dye compound obtained colorscelluloseacetate a violet .1 gram mole of diazotized,l-amino-2,4-dinitro-fi-chlorobenzene is coupled with .1 gram mole o1l-4,5-dihydroxyamylamino-naphthalene. The dye compound obtained colorscellulose acetate blue shades.

Erma: l0

.1 gram mole of diazotizedl-amino-2,4-dinitrobenzene-fi-monoethylsuli'oneamide is coupled with .1gram mole of N-4,5-dihydroxyamyl-'I- methyltetrahydroquinoline. The dyecompound obtained has the formula:

' cn'icmcmcncmon so 1 H ER: all: H:

and colors cellulose acetate deep blue shades.

Exsirrts 11 .1 grain mole oi diazotized paminoa.zobenzene is coupledwith .1 gram mole of l-(p,-y-dihydroxypropyl-, 4,5-dihydroxyamyl-) amino3-methoxybenzene. The dye compound obtained has the formula:

and colors cellulose acetate red shades.

' EXAITLI 12 .1. gram mole of the am compound 4' nitrobenzeneazo (1.1")-4-bis-4,5-dihydroxyamylaminobenzene is dissolved in 4 liters ofmethanol and is reduced under reflux with 4 gram moles 01 sodiumsulfide. After 3 hours the nitro group is reduced to an amino group andthe dye compound resulting is recovered by adding water to the reactionmixture and filtering. The precipitated dye is washed with water anddried. It colors cellulose acetate orange-yellow shades. This dye can beapplied to the textile fabrics indicated 'hereinbei'ore and whendiazotized and developed on fiber. with 2-hydroxy-3-naphthoic acid givesvaluable black shades.

Exam: l3

.1 gram mole of diazotized p-nitroaniline is coupled with .1 gram moleoi N-4,5-dihydroxy-v amyl-2-methylbenzothiomorpholine. The dye compoundobtained has the formula:

and colors the textile materials indicated hereinbefore red shades.

Emma: 14

.1 gram mole of diazotized a-aminonaphthalene is coupled with .1 grammole of 4,5-dihydroxyamylaniline. The dye compound obtained. colorsorganic derivatives of cellulose, wool, silk and nylon yellowish-orangeshades.

EXAMPLE 15 .1 gram mole of diazotized 2-amino-5-nitrobenzenesulfonicacid is coupled with .1 gram mole of (ethyl-,4,5-dihydroxyamyD-aminoben-' zene. The dye compound obtained colors wooland silk rubine shades.

EXAMPLE l6 .1 gram mole of diazotized 3-'chloro-4-aminobenzenesulfonicacid is coupled with .1 gram mole of1-4,5-dihydroxyamylamino-5-hydroxynaphthalene. The dye compound obtainedcolors wool and silk orange shades.

EXAMPLE 17 .1 gram mole of diazotized l-naphthylamine- -sulfonic acid iscoupled with .1 gram mole of 1-4,5 dihydroxyamylamino 3 methylbenzene.The dye compound obtained colors wool and silk orange shades;

Emma: 18

.1 gram mole of diazotized p-aminoacetophenone is coupled with .1 grammole of 1-4,5-dihydroxydihydrobenzopyrazole. The dye compound obtainedhas the formula:

CHCHCHIOHCHIOH It colors organic derivatives of cellulose, wool,

" silk and nylon orange shades.

, silk and nylon rubine shades.

EXAMPLE 19 ...1 gram mole of diazotized p-nitroaniline is coupled with.1 gram mole of 1-4,5-dihydroxyamyI-G-methylindoline. The dye compoundobtained has the formula:

. (FHzCHnCHrCHCHaOH CHI /N\ H It colors organic derivatives ofcellulose, wool,

Amine Coupling component Color p-Aminoacetuf (1) 1-(fiyy-dihydroxypropyb,4,E dihydroxyamy1 )amino- Yellowish-orange.

3-ehlorobenzene. Dn (2) e(4,5rdihydroxyarnyl-, fihydtoxyethyl-mminoben-Orange. 1 no. Dn (3 N-4 b-dihydroxyamyldiphenylemine D D g4;Ethyb,4,5-dihydroxyamyl-)aminobenzene D8, D0 5) -hydroxypropy1-,4,5-d1hydroxyamyl-)amino-2- D methoxybenzene, (6) (Allyb,4,5-d1hydroxyamy1-)amino-2-methoxy-5- Orange-red.

methylbenzene. (7) (p-gnethoxyethyb, 4,5-dihydroxyamyl-) amino- D2,5-d1methoxybenzene. (8) (B-suliatoethyl-, 4,5-d.1hydroxyamyl-)amino-2- D methoxy-li-methylbenzene. 9)thl-1(fl-sulIoethyl-,4,5'dihydroxyamyl-) eminonaph- Red, i a cue. p-Aminophenyl-methylsulione1-9 above 0 p-Nitroaniline rlo 032g:- :3 11531-amincg-ghoro-i-rgtrglienggne "go..." n l-aminoinitro- -c are nzene o.2-amino-3,5-dinitrophenylmonoethylsulfonamide do i to blue'green'l-arninc-2,4-dinitro-6-hydroz benzene .do a-naphthylamme do Orange toviolet. p-Nitroamh (10) B o-dihydroxyamylammo-3-chlorobenzene Orange.

Do (11) Bis-afi'dihydroxyamylaniline o Do (12) Bs-4,fi-drhydroxyamylamino-Zi-methoxybenzene. Red. Do (13)B15-4,6-d1hydroxyamyl-2-methoxy-5chlorobenzene.l Do. Do (1%Bis-4,5-dihydroxyamylamino-2-methoxy-5-methyt Rubine enzene. Do (15)Bis-4,5-dihydroxyamylamino:2,5-dimethoxybenzene. Do (16;1-bis-4,5-dihydroxyamylaminonaphthalene Do (IZ a I-bi:-4,fi-d ydmxya ylaino-o-hydroxynaph Bl en l-amino-2-chloro-4-nitrobenzene4-nitrobenzeneazo-4-aminobenzene fij bluel-amino-g-b3droy--ritrob%nzene. D0 l-amino- 4- ini roromo enzenel-emino-ii-dinirgg-cganogznzene d to blue green 1-5mino-4-ni roic oronzene o B p-Aminoecetophenone 18)4,fi-dihydroxyamylemino-2-chlorobenzene f. i.fif,3.f

Do 19) 4,5-d hydroxyamylamino-z-fluorobenzene Do 204,5-d1hydr0xyamylamm0-2-methylbenzene Yen0WiSh-]'ange Dn 214,Mlihydroxyamylammo-2-methoxybenzene Orange. Do 1 3,5-d v xya y1a no-methoxy-5-acetylam- Rubine,

o nzene. 1 23) 1-4,5-dihydroxyamylamino-5-hydroxynaphthAlene. D Do......gfl g l go-dihydroxyamylamino-fi-acetylaminonaphthe- D v aaeaeee Am!!!Coupling component Color p-Aminophenylmetbylsulione 18-24 abov Orange toviolet. o-Aminophonylmethylmllonn (In Do. p-Aminouobenzen do Orange tored-blue. o-Nitroanilin do Orange to violet.i-amino-2-methyl-d-nitrobenzen do Orange to blue.l-amino-i-ethoxyd-nltrobenzene. v n Do.z-amino-s-nitmphenylmethylsulione n Orange to blue-green.2-amino-ii-nitrophenylmethylketon n Do. l-emino-fl-oyano-d-nitrobenzemudo Do. p-Aminoecetophenone (25) N, fdihydroxyamyl-2-methyl-1,2,3,4-tetrahy- Orange.

(it o e. no as -4,5-dlhydoxyamylbenzomo holine Do. 2'! N-4,5-dilioxyamyl-2-methy benzomorpholinenn Do. TM 28 N-4,6-dydroxyamyl-z-methylbennoth omorpho- Do. e. Tin 29 14,6dihdroxyamyldihydrobanzopyrazole....- Do. n to; N4 6-ydroxyamyl-7-methyl-1,2,3,4-teinhydro- Red.

1 uinoli'ne. I m 1 N-4,6-dihydroxyamyl-7-methylbenzomorpholine..-- Do. D32 N-M-dlhydroxyamyl-d-methylindo e Do. D 3% N4,6-ugih]ndroxyamyl-7-aeetylamino-l,2,3,4-tetra- Rubine.

ydmq o e. no (314 N-4,6-dihydroxyamyl-7-acetylaminobenzomorpho- Do.

0. a 'Dn (3i5 N-4,5-dihydroxyamyl-B-acetylaminobenzomorpho- Do. 0. D(36) N-4,6-dihydroxyamyl-5-acetylamino-l,2,3,4-tetra- Do.

h v droquinoline. p-Nitmnniline... abov Red to whine. z-arnino-dgi trgphenylmeth lsulic v 0 Red to violet. l-amino-il, tro-o-ehloro e r nRed-blue. z-aminoao-dinitrophenylethylmlfon r n Greenish-blue.3'-nitrobenzeneazo-4-a o do.--.. Ruhine. l-amino-flA-dinitronapbthalendo.-. Blue. 1 -amigo-4-nitrobenzene-6-mono -p-methoxyathylsulfone- 1-9above- Rubine to violet.

e. Dn- -17 abov Do. Tin 18-24 abov Do. B -36 above Do.l-amino-Zl-diultrobennane-B -mono -p methoxy ethyl 1-9 above Rubine toblue-green.

snlioneamide.

Dn 10-17 above Do. D 18-24 above-.- .1 Do. Dn 25-36 above. Blue toblue-green. 1 amino -4 -nltrobenzane 6 -mono p hydroxyethyl sul 1-9above Bad to blue-green.

ioneamide.

Dn 10-17 above Do. 1 -amino-2,4-dinitrobentene -6-mono -fl -hydroxyethyl18-24 above Do.

aulioneamide.

It will be understood that the foregoing examples are intended to beillustrative and not limitative of our invention or discovery. Thediazonium compounds of any of the amines indicated herein can becoupled, for example, with any or the coupling components indicatedherein to yield dye compounds of the invention or discovery. Additionalamines-that can be diazotized pounds of our invention or discovery maybe,

entirely clear, the preparation of the 4,5-dihydroxyamyl intermediatesemployed 'in their manufacture is indicated hereinafter. These compoundscan be prepared by reacting the coupling components of the characterindicated hereinbefore, minus the 4,5-dihydroxyamyl group, with thediacetate of 1-chloro-4,5-dihydroxy-npentane, that is,1-chloropentane-4,5-diol diacetate having the formula:

cicmcmcmcrrc'mo-ccm Q separating the compound formed and hydrolyzing itto the desired 4,5-dihydroxyamyl intermediate. Thus, aminobenzene,aminonaphthalene, 1,2,3,4-tetrahydroquino1ine, benzomorpholine,benzothiomorpholine, diphenylamine, dihydrobenzopyrazole and indolinecompounds containing a replaceable hydrogenatom on the nitrogen atom,for example, can be so treated to introduce a 4,5-dihydroxyamyl groupwhich is directly 80 attached to the nitrogen atom. In the case of thesecompounds containing a nitrogen atom having two replaceable hydrogenatoms, two 4,5- dihydroxyamyl groups can be prepared.

The diacetate of l-chloro-4,5-dihydroxy-npentane (chlorodiacetate1,4,5-pentane) can be prepared as described in Comptes rendus, vol. 211,page 645 (1940). This compound can also be obtained in substantiallypure form by the 01- lowing procedure:

204 grams of tetrahydrofurfuryl alcohol, 500 grams of acetyl chlorideand a few milligrams of zinc chloride are placed in a suitable reactionvessel and subjected to a refluxing operation for one hour. The reactionmixture is then distilled under reduced pressure and the fraction comingoff at 157 C.-158 C./20 mm, is separately recovered. The run wasrepeated. 656 grams of the fraction distilling off at 157 C.-l58 (1/20mm. were obtained from the two runs. This fraction consists principallyof the diacetate of l-chloro- 4,5-dihydroxy-n-pentane together with aminor 1| amount of the diacetate of 4-chloro-1,5-dihydroxy-n-pentane. Acarbon, hydrogen, chlorine analysis gave the following results:

Cgllculstcdtfor 1- M0 11 ane- Fmmd 4.5-(831 diacetate 0. 47.90 48.65 i Huse 0.75 01 15.58 15.97

800 grams 0! the reaction mixture obtained were fractionated in aiacketed, helix packed lraotionatlng column capable oi closefractionation with the results tabulated hereinafter.

Fractions Boiling point Grams 85-122/12 mm 18 122-141/12 mm 28141-148/12 mm 11 148-151/12 mm 230 The fraction boiling at 141-148/12mm. consists almost entirely of 4,5-diol diaoetate).

Preparation of N -4,5-dihydroxyamyl-2-methyl-1,2,3,4-tetrahydroquinoline 14.7 grams of2-methyl-1,2,3,4-tetrahydroquinoline, 25.0 grams of1-chloropentane-4,5-diol 'diacetate and 63.0 grams of NazCOa are placedtogether in a suitable reaction vessel and heated with stirring for 5hours in an oil bath at 200 C. Upon cooling 50 cc. of ethyl alcohol wereadded to the reaction mixture and the salt formed in the reaction wasremoved by filtration. The reaction mixture was then distflled. About$6; of the mixture was unreacted 2-methyl-l,2,3,4-tetrahydroquinolineand 1-chloropentane4,5-diol diacetate, which were removed bydistillation under reduced pressure. The portion remainingconsistsessentially of the 4,5-diacetate of N-4,5-dihydroxyamyl-2-methyl-1,2,3,4tetrahydroquinoline and is a quite viscous material boiling at 2l5225C./9 mm.

- 5 grams of the diacetate ofN-4,5-dihydroxyamyl-2-methyl-1,2,3,4-tetrahydroquinoline obtained asabove were heated on the steam bath for 3 hours with cc. of 1:6 H2804.The reaction mixture was then made alkaline with NazCOa and extractedwith benzene. The benzene extract was then washed with water and thesolvent was removed by distillation under reduced pressure leavingN-4,5-dihydroxyamyl-2-methyl-1,2,3,4- tetrahydroquinoline.

Preparation of i-(p-hydroxyethyb, 4,5-dihydrprcyamyb)amino-3-methylbenzene 15.1 grams of1-,B-hydroxyethylamino-3-methylbenzene, 25.0 grams of1-chloropentane-4,5- diol diacetate and 63.0 grams of NazCOa are placedtogether in a suitable reaction vessel and heated with stirring for 5.hours in an oil bath at 180190 0. Upon cooling, 50 cc. of ethyl alcoholwere added to the reaction mixture and the salt formed in the reactionwas removed by filtration. The

the diacctate oi l-chloro-4,5-dihydroxy-n-pentane(l-chloropentanereaction product was then distilled under reducedpressure to remove unreacted l-chloropentane- 4,5-diol diacetate and1-(p-hydroxyethyl-, 4,5- dihydroxyamyl-)amino-a-methylbenzene. Theportion remaining consists essentially of the 4,5-

diacetate of l-(p-hydroxyethyh, 4,5-dihydroxyaddition of sodiumhydroxide and the oil that separates is extracted with ether. The etherextract was then distilled under reduced pressure, the ether being firstremoved in this distillation, to obtain a good yield of1-(p-hydroxyethyl-, 4,5- dihydroxyamyl-) amino-B-methylbenzene whichboils at 245-250 0J4 mm.

90 Preparation of 1-bis-4,5-dihydroxyamylamino-3- methwlbenzene .1 grammole of m-toluidine is heated with stirring in a suitable reactionvessel at 150-180 C.

Compound Boiling point l-4,B-diacetoxyamylaminonaphthalene1-4,ddihydroxyamylaminonaphthalenel-4,5-diacetoxyamylsmino-2-methoxy-5-methylbenzene.

1 4 5 dihydroxyamylammo- 2- methoxy l5 methylbenzene.

N-4,5-di ace toxyam yl-7-methyltetrahydroquinoline.N-4,5-dihydroxyamyl-7-methyltetrahydroquinoline.

252-257" C./4 mm. 240-250 0.14 mm. 220-235 0J4 mm.

194-198 c./a mm.

215-218 0J4 mm.

221223 C./4 mm.

From the examples that have been given, the manner of preparation of thecoupling components usedin the manufacture of the azo dye compounds ofour invention or discovery will be apparent since the procedureindicated is applicable to the preparation of all of the variouscoupling components disclosed herein.

The azo compounds of our invention are, for the most part, relativelyinsoluble in water and, accordingly, they may be advantageously directlyapplied to the material undergoing coloration in the form of an aqueoussuspension which can be prepared by rinding the dye to a paste in thepresence of a sulfonated oil, soap or other suitable dispersing agentand dispersing the resulting paste in water. In some instances. the dyemay possess sufllcient solubility in water as to render the use of adispersing agent unnecessary. Generally speaking, however, the use of adispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted attemperatures of about iii- C. but any suitable temperature may be used.Thus, the textile material to be dyed or colored is ordinarily added tothe dyebath at a temperature lower than that at which the main portionof the dyeing is to be effected. a temperature approximating 45-55 C.,for example, following which the temperature is raised to that selectedfor carrying out the dyeing. operation. The temperature at which thedyeing is conducted may, of course, be varied somewhat depending uponthe particular material undergoing coloration. As isunderstood by thoseskilled in the art, the intensity of dyeing can be varied by varying theproportion of dye to material undergoing coloration. Generally speaking,1-3% by weight of dye to material is employed although any desiredproportions can be used.

Suitable dispersing agents together. with the amounts that may beemployed are disclosed in our U. S. Patent No. 2,115,030, issued April26,

- 1938. The process disclosed in this patent for the dyeing of celluloseacetate can be used in applying the dyes of the present application tothis material. While a satisfactory method of dyeing has been disclosedherein, it will be understood that any other suitable methods for dyeingthe non-vegetable textile materials named herein can be employed.Lacquers may be colored with the dye compounds of our invention by themethods customarily employed in the lacquer art.

2. The azo compounds having the formula:

RN=N-R1 atom having a'fused-on. benzene ring and in which a heteronitrogen atom is directly attached to the fused-on benzene ring andG-membered heterocyclic coupling components containing at least onehetero nitrogen atom having a fusedon benzene ring and in which a heteronitrogen atom is directly attached to the fused-on benzene ringcontaining a 4,5-dihydroxyamyl group joined directly to its nucleusthrough a nitrogen atom.

3. The azo compounds having the formula:

Rr--N=N-R1 wherein R represents the residue of a member selected fromthe group consisting of a benzene It is here noted that the term "nylon"refers to a linear polyamide resin which is believed to be basicallydescribed or claimed in U. S. Letters Patent 2,071,250, issued February16, 1937, to Wallace H. Carothers.

The fractionation of the reaction mixture resulting from the reaction oftetrahydroiurfuryl alcohol, acetyl chloride and zinc chloride describedhereinbefore can be carried out in a highly efllcient distillationcolumn (see Whitmore and Lux, Journ. Am. Chem. Soc. 54, 3453 (1932);Fenske, Tongberg and Quiggle, Ind. Eng. Chem. 26, 1169 (1934); Tongberg,Quiggle and Fenske, Ind. Eng. Chem. 26, 1213 (1934) and W. W. Stewart,Ind. Eng. Chem. 28, 451 (1936)). The distillation columns described inthe articles referred to can, of course, be used to effect any of thefractionation operations required in connection with the presentinvention or discovery.

1:6 H1504 as used herein refers to a mixture of 1 part of concentratedsulfuric acid (94-95% -H2SO4) and. 6 partsof water, the parts being byweight.

We claim: 1. The azo compounds having the formula:

wherein R represents the residue of a member selected from the groupconsisting of a benzene nucleus, a, naphthalene nucleus andan azobenzenenucleus and R1 represents the residue of a coupling component selectedfrom the group consisting of coupling components of the benzene series,coupling components of the naphthalene series, S-membered heterocycliccoupling components containing at least one hetero nitrogen atom havingafused-on' benzene ring and in which a, hetero nitrogen atom is directlyattached to the fused-on benzene ring and G-membered heterocycliccoupling componentscontaining at least one hetero nitrogen atom having afusedon benzene ring and in which a hetero'nitrogen atom is directlyattached to the fused-on benzene ring and wherein at least one of themembers R and R1 contains a 4,5-dihydroxylamyl group joined directly tothe nucleus through a nitrogen atom.

nucleus, a naphthalene-nucleus and an azobenzene nucleus and R1represents the residue of a benzene coupling component containing aij-dihydroxyamyl group joined directly to its nucleus through a nitrogenatom. 4. The azo compounds having the formula:

RN=N-R1 wherein R represents the residue of a benzene nucleus and R1represents the residue of a benzene coupling component containing a4,5-dihydroxyamyl group Joined directly to its nucleus through anitrogen atom.

5. The, nuclear non-sulfonated monoazo dye compounds having the formula:

I RN=NR1N ontomcmonomon R -N=N-'R -'N CHICHIOHICHCHiOH wherein R standsfor the residue of abenzene nucleus and R1 stands for the residue of abenzene nucleus.

'7. The nuclear non-sulfonated monoazo dye compounds having the formula:

R-N=NR1.

' whereinR stands for the residue of a benzene 8 I 2,350,599 I I 8. Theazo dye compound having the formula; 10. Thu! azo dye compound havingthe formula:

/CH:CH|0H CHaCHaGHaCHOHaOH N0 Nm N H n cn on on 011011 B N\ n a; c-cn.

, H H: 9. The azo dye compound having the formula: g

H N-CBaCHaCHzCHCBaOH to JOSEPH B. DICKEY.

JAMES G. MCNALLY.

H O= n-N-CBaCHaOCHa

